1. Field of the Invention
The present invention relates to epoxy derivatives useful as starting materials for synthesizing various physiologically active materials and a method of producing the derivatives, cyclohexanone derivatives, cyclohexenone derivatives, 3-substituted cyclohexanone derivatives, and a method of producing optically active carvone of perfume via these derivatives.
2. Description of the Prior Art
Epoxy derivatives, cyclohexanone derivatives, and 3-substituted cyclohexanone derivatives of the present inventions are widely useful as starting materials for synthesizing various physiologically active materials such as medicines and agricultural medicines, particularly these derivatives are very useful as starting materials for synthesizing optically active carbons of perfumes and their intermediates. Hitherto, a method for efficiently introducing substitution groups stereoselectively into cyclohexa-2, 5-diene skeletons (6) is unknown. For example, as a conventional method of optically active carvones, a reaction method of hydration of d-limonene with synthetic zeolite (Nihon Kagakukaishi, (1) , pages 63-67 (1992)), a method of stereoselective Grignard reaction with optically active 5-trimethylsilyl-2-cyclohexenone as a starting material (Takei et al, Tetrahedron Lett., 30, 7075 (1989)) and the like have been known. The former method is not stereoselective in the reaction, so that optically active carvone should be isolated from five kinds of products, the steps are troublesome and the product is obtained in low yield (30%). The latter method is stereoselective, but optically active 5-trimethylsilyl-2-cyclohexenone, which is a starting material having a stereoselectively 5-substituted group, should be obtained by repeated recrystallization of a diastereomer salt synthesized from a racemate of the starting material with cinchonidine and toluenethiol, and it is obtained in a low yield of 3% from racemic-5-trimethylsilyl-2-cyclohexenone. Thus, prior to the present invention, there is no industrially excellent method for producing efficiently optically active carvones.
Accordingly, it is desired to find an efficient method for producing optically active carvones. Further, it is desired to find optically active intermediates such as epoxy derivatives of the present invention obtained by deriving stereoselectively a substituted group, cyclohexanone derivatives, cyclohexenone derivatives, and 3-substituted cyclohexanone derivatives, which are widely applicable.